US3932188A - Silver halide photographic lightsensitive material - Google Patents
Silver halide photographic lightsensitive material Download PDFInfo
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- US3932188A US3932188A US05/552,262 US55226275A US3932188A US 3932188 A US3932188 A US 3932188A US 55226275 A US55226275 A US 55226275A US 3932188 A US3932188 A US 3932188A
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- dye
- silver halide
- halide photographic
- lightsensitive material
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- -1 Silver halide Chemical class 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 18
- 239000004332 silver Substances 0.000 title claims abstract description 18
- 239000000975 dye Substances 0.000 claims abstract description 59
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 28
- 239000000839 emulsion Substances 0.000 claims description 20
- 239000011247 coating layer Substances 0.000 claims description 4
- 101001022148 Homo sapiens Furin Proteins 0.000 abstract 1
- 101000701936 Homo sapiens Signal peptidase complex subunit 1 Proteins 0.000 abstract 1
- 102100030313 Signal peptidase complex subunit 1 Human genes 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000005316 response function Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical class [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- MCBBJCJHHDKGHB-UHFFFAOYSA-N 2-[3-(4-nitrophenyl)-5-oxo-4H-pyrazol-1-yl]benzene-1,4-disulfonic acid Chemical compound [N+](=O)([O-])C1=CC=C(C=C1)C1=NN(C(C1)=O)C1=C(C=CC(=C1)S(=O)(=O)O)S(=O)(=O)O MCBBJCJHHDKGHB-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical group OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 101001128694 Homo sapiens Neuroendocrine convertase 1 Proteins 0.000 description 1
- 101000601394 Homo sapiens Neuroendocrine convertase 2 Proteins 0.000 description 1
- 101001072067 Homo sapiens Proprotein convertase subtilisin/kexin type 4 Proteins 0.000 description 1
- 101000828971 Homo sapiens Signal peptidase complex subunit 3 Proteins 0.000 description 1
- 101000979222 Hydra vulgaris PC3-like endoprotease variant A Proteins 0.000 description 1
- 101000979221 Hydra vulgaris PC3-like endoprotease variant B Proteins 0.000 description 1
- 102100032132 Neuroendocrine convertase 1 Human genes 0.000 description 1
- 102100037732 Neuroendocrine convertase 2 Human genes 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 108010022052 Proprotein Convertase 5 Proteins 0.000 description 1
- 102100036371 Proprotein convertase subtilisin/kexin type 4 Human genes 0.000 description 1
- 102100036365 Proprotein convertase subtilisin/kexin type 5 Human genes 0.000 description 1
- 102100038946 Proprotein convertase subtilisin/kexin type 6 Human genes 0.000 description 1
- 101710180552 Proprotein convertase subtilisin/kexin type 6 Proteins 0.000 description 1
- 102100038950 Proprotein convertase subtilisin/kexin type 7 Human genes 0.000 description 1
- 101710180647 Proprotein convertase subtilisin/kexin type 7 Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- NGRXSVFCLHVGKU-UHFFFAOYSA-N ethyl 3-(4-nitrophenyl)-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=C([N+]([O-])=O)C=C1 NGRXSVFCLHVGKU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical group O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
Definitions
- the present invention relates to a silver halide photographic lightsensitive material containing a dye and more particularly it relates to a silver halide photographic light sensitive material prevented from irradiation and halation.
- dyes which absorb undesired reflected light, scattered light, diffused light in lightsensitive emulsion layer or undesired reflected light from boundary face between the emulsion layer and a support and back face of the support are contained in a silver halide photographic light sensitive material to prevent irradiation and halation, thereby to increase sharpness of the obtained photographic image.
- the dyes used in the lightsensitive emulsion layer between the lightsensitive emulsion layer and the support or in the back coating of the support for preventing irradiation and halation must not cause fading or discoloration during preparation of solution or must not cause change with lapse of time during preparation of the lightsensitive emulsion and storage. Furthermore, such dyes must not have adverse effect on photographic characteristics such as fog, decreasing of sensitivity, etc. Moreover, they must be completely and rapidly decolorized and removed from photosensitive material during photographic developing process. They must have appropriate spectral absorption characteristic which corresponds to respective object of use and exhibit effect of preventing irradiation and halation.
- X represents hydrogen atom, hydroxyl group, a lower alkyl group or a halogen atom
- L represents a methine group which may be substituted with lower alkyl group at mesoposition
- M represents hydrogen atom, an alkali metal or ammonium group and n is 1 or 2).
- Silver halide photographic lightsensitive materials colored with the methine oxonol dyes represented by the above general formula possess a wide absorption band in objective absorption wave length region and have substantially no unnecessary absorption in other wave length region. Furthermore, when n is 2 and 3-position of the pyrazolone ring is p-nitrophenol group, the absorption maximum of present pentamethine oxonol dyes shifts to longer wave length side than there which was proposed in Japanese Patent Publication No. 22069/64. So especially, when said pentamethine oxonol dyes of the present invention are used in color lightsensitive materials, they are markedly useful as irradiation preventing dyes for red sensitive emulsion layer including cyan coupler.
- the dyes used in the present invention have no adverse effect on photographic characteristics such as fog, decreasing of sensitivity, etc. and in addition, they are completely and rapdily decolorized and dissolved out from lightsensitive materials after developing process to cause no coloration of the photographic image due to residue of the dyes used. Furthermore, the dyes used in the present invention show no fading and discoloration during preparation of dye solution and are not utterly influenced by external conditions such as humid heat during preparation of lightsensitive emulsion and storage.
- the methine oxonol dyes used in the present invention are not limited to the above exemplified dyes, but any dyes having the chemical structure represented by the general formula may be used. If necessary, they may be used in admixture of two or more.
- dyes having three methine chains may also be synthesized in the same manner as above except malondialdehydedianil hydrochloride is substituted for glutacon dialdehydedianil hydrochloride.
- dyes having the general formula as given above are added preferably in the form of an aqueous solution to silver halide emulsion or protective colloid solution.
- Amount of the dye used in the present invention is preferably about 1 mg -- about 10 g/m 2 .
- the amount is less than about 1 mg/m 2 , effect of preventing irradiation is extremely small and when the amount is more than about 10 g/m 2 , unfavorable reduction in photographic sensitivity is caused and moreover elimination of the dye by photographic treatments cannot be completely attained.
- the dyes used in the present invention have effects of preventing irradiation and halation.
- the dye is preferably added in an amount of about 1 mg -- about 100 mg/m 2 to at least one layers of the silver halide emulsion layer, the intermediate layer and the overcoating layer.
- the dye is preferably added in an amount of about 10 mg -- about 10 g/m 2 to at least one layers of undercoating layer and back-coating layer of the suppert.
- a blue sensitive silver iodochlorobromide emulsion layer (silver bromide . . . about 98 mol %) containing a yellow coupler having the following formula: ##SPC4##
- Said emulsion layer additionally contained the usual stabilizer, hardener, wetting agent for coating, etc.
- An intermediate layer comprising 4% aqueous solution of gelatin.
- a green sensitive silver chlorobromide emulsion layer (silver bromide . . . about 35 mol %) containing the following magenta coupler. ##SPC5##
- An intermediate layer comprising 4% aqueous solution of gelatin.
- a red sensitive silver chlorobromide emulsion layer (silver bromide . . . about 35 mol %) containing the following cyan coupler. ##SPC6##
- a protective layer having the same compositions as the layers (2) and (4).
- Sample No. 2 was prepared in the same manner as of preparation of the Sample No. 1 except that 50 ml of 2% aqueous solution of the dye (IV) enumerated hereinbefore was added to 1 kg of the red sensitive silver chlorobromide emulsion used in preparation of the sample No. 1.
- Samples No. 1, 4 and 5 were exposed and then subjected to the same processes as in Example 1. Thereafter, density of unexposed areas of these samples was measured. As shown in the following table, the sample containing the present dye was rapidly decolorized and showed no color stain.
- the density in the Examples was measured by Macbeth 514 densitometer.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Irradiation and halation of a silver halide photographic lightsensitive material can be prevented by adding at least one of dyes represented by the following general formula to the layers on one or both sides of the light sensitive material. ##SPC1##
(wherein X is hydrogen atom, hydroxyl group, a halogen atom or a lower alkyl group, L is a methine group which may be substituted with a lower alkyl group at mesoposition, M is hydrogen atom, an alkali metal or ammonium group and n is 1 or 2).
Description
The present invention relates to a silver halide photographic lightsensitive material containing a dye and more particularly it relates to a silver halide photographic light sensitive material prevented from irradiation and halation.
It is well known that dyes which absorb undesired reflected light, scattered light, diffused light in lightsensitive emulsion layer or undesired reflected light from boundary face between the emulsion layer and a support and back face of the support are contained in a silver halide photographic light sensitive material to prevent irradiation and halation, thereby to increase sharpness of the obtained photographic image.
It is natural that the dyes used in the lightsensitive emulsion layer between the lightsensitive emulsion layer and the support or in the back coating of the support for preventing irradiation and halation must not cause fading or discoloration during preparation of solution or must not cause change with lapse of time during preparation of the lightsensitive emulsion and storage. Furthermore, such dyes must not have adverse effect on photographic characteristics such as fog, decreasing of sensitivity, etc. Moreover, they must be completely and rapidly decolorized and removed from photosensitive material during photographic developing process. They must have appropriate spectral absorption characteristic which corresponds to respective object of use and exhibit effect of preventing irradiation and halation.
Considerably a large number of dyes have been proposed, but substantially none of them meet the requirements on photographic characteristics, decolorizability and removability and absorption characteristic.
The inventors have found that the methine oxonol dyes having the following general formula satisfy the above requirements and have effect of preventing irradiation and halation. ##SPC2##
(wherein X represents hydrogen atom, hydroxyl group, a lower alkyl group or a halogen atom; L represents a methine group which may be substituted with lower alkyl group at mesoposition; M represents hydrogen atom, an alkali metal or ammonium group and n is 1 or 2).
Silver halide photographic lightsensitive materials colored with the methine oxonol dyes represented by the above general formula possess a wide absorption band in objective absorption wave length region and have substantially no unnecessary absorption in other wave length region. Furthermore, when n is 2 and 3-position of the pyrazolone ring is p-nitrophenol group, the absorption maximum of present pentamethine oxonol dyes shifts to longer wave length side than there which was proposed in Japanese Patent Publication No. 22069/64. So especially, when said pentamethine oxonol dyes of the present invention are used in color lightsensitive materials, they are markedly useful as irradiation preventing dyes for red sensitive emulsion layer including cyan coupler.
The dyes used in the present invention have no adverse effect on photographic characteristics such as fog, decreasing of sensitivity, etc. and in addition, they are completely and rapdily decolorized and dissolved out from lightsensitive materials after developing process to cause no coloration of the photographic image due to residue of the dyes used. Furthermore, the dyes used in the present invention show no fading and discoloration during preparation of dye solution and are not utterly influenced by external conditions such as humid heat during preparation of lightsensitive emulsion and storage.
Representative examples of the dyes represented by the above general formula are as follows: ##SPC3##
The methine oxonol dyes used in the present invention are not limited to the above exemplified dyes, but any dyes having the chemical structure represented by the general formula may be used. If necessary, they may be used in admixture of two or more.
A method for synthesizing the dye (IV) will be explained below.
1. 2.37 g of ethyl-p-nitrobenzoylacetate (disclosed in H. F. Ginsberg et al "Journal of the American Chemical Society" Vol. 75, Page 4587, 1953) and 2.68 g of phenylhydrazine-2,5-disulfonic acid in 60 ml of 50% acetic acid are heated at 95°-100°C for 8 hours. Then, the solvent is concentrated under reduced pressure and ethanol was added to the residue, then the solid was collected on a Buchner funnel and dried to obtain 3.01 g of a light yellow solid having a melting point above 300°C.
2. 1.94 g of above obtained 3-(4-nitrophenyl)-1-(2,5-disulfophenyl)-5-pyrazolone and 0.57 g of glutacondialdehydedianil hydrochloride are suspended in 40 ml of methanol, to which 1.61 g of triethylamine is added and refluxed for 30 minutes. The dye solution obtained is concentrated under reduced pressure. Then, 40 ml of ethanol is added and refluxed for 5 minutes. The dye separated upon warming is collected on a Buchner funnel. Said ethanol washing is repeated further 2 times and then the dye is dried to obtain 0.86 g of dark blue dye (IV) having a melting point above 300°C. Absorption maximum of an aqueous solution of the dye is 640 mμ. u.
Other dyes having three methine chains [e.g., dyes (I), (II) and (III)] may also be synthesized in the same manner as above except malondialdehydedianil hydrochloride is substituted for glutacon dialdehydedianil hydrochloride.
Thus obtained dyes having the general formula as given above are added preferably in the form of an aqueous solution to silver halide emulsion or protective colloid solution.
Amount of the dye used in the present invention is preferably about 1 mg -- about 10 g/m2. When the amount is less than about 1 mg/m2, effect of preventing irradiation is extremely small and when the amount is more than about 10 g/m2, unfavorable reduction in photographic sensitivity is caused and moreover elimination of the dye by photographic treatments cannot be completely attained.
The dyes used in the present invention have effects of preventing irradiation and halation. When prevention of irradiation is desired, the dye is preferably added in an amount of about 1 mg -- about 100 mg/m2 to at least one layers of the silver halide emulsion layer, the intermediate layer and the overcoating layer. When prevention of halation is aimed at, the dye is preferably added in an amount of about 10 mg -- about 10 g/m2 to at least one layers of undercoating layer and back-coating layer of the suppert.
The following working examples illustrate formation of an irradiation preventing layer and a halation preventing layer with use of the dyes according to the present invention.
The following layers were succesively coated on a photographic support on which polyethylene was laminated to obtain a multilayer color photographic paper (Sample No. 1).
1. A blue sensitive silver iodochlorobromide emulsion layer (silver bromide . . . about 98 mol %) containing a yellow coupler having the following formula: ##SPC4##
Said emulsion layer additionally contained the usual stabilizer, hardener, wetting agent for coating, etc.
2. An intermediate layer comprising 4% aqueous solution of gelatin.
3. A green sensitive silver chlorobromide emulsion layer (silver bromide . . . about 35 mol %) containing the following magenta coupler. ##SPC5##
4. An intermediate layer comprising 4% aqueous solution of gelatin.
5. A red sensitive silver chlorobromide emulsion layer (silver bromide . . . about 35 mol %) containing the following cyan coupler. ##SPC6##
6. A protective layer having the same compositions as the layers (2) and (4).
Sample No. 2 was prepared in the same manner as of preparation of the Sample No. 1 except that 50 ml of 2% aqueous solution of the dye (IV) enumerated hereinbefore was added to 1 kg of the red sensitive silver chlorobromide emulsion used in preparation of the sample No. 1.
In the same manner as mentioned above, sample No. 3 having 50 ml of 2% aqueous solution of the following known dye A was prepared. ##SPC7##
These samples were exposed and then treated with the following processing solutions.
______________________________________
Color developing solution (abbreviated as CD).
Benzyl alcohol 15 ml
KBr 0.3 g
Sodium hexametaphosphate 0.5 g
Sodium sulfite 2.0 g
Hydroxylamine hydrochloride 2.0 g
Sodium carbonate (monohydrate)
28.0 g
CD-3* 4.8 g
Water to make 1000 ml
*Trade name for color developer produced by Estman Kodak Co.
Bleaching and fixing solution (abbrivated as BF)
EDTA iron salt 62 g
EDTA-2-sodium salt 3 g
Ammonium thiosulfate 75 g
Sodium sulfite 10 g
Sodium carbonate (monohydrate)
5 g
Water to make 1000 ml
Stabilizing solution (abbrivated as SB)
45% acetic acid 19 ml
Sodium acetate 3 g
Water to make 1000 ml
______________________________________
All processings were conducted at a high temperature and a high speed in accordance with the conditions enumerated in the following table.
______________________________________
Temperature Processing time
______________________________________
CD 33°C 3 minutes and
30 seconds
BF " 1 minute and
30 seconds
Washing with " 2 minutes
water
SB " 30 seconds
Washing with " 15 seconds
water
Total 7 minutes and
45 seconds
______________________________________
Density of unexposed areas of each sample after subjected to the above process was measured. The results are shown in the following table.
______________________________________
Density of unexposed area
Sample Dye Blue Green Red
density density density
______________________________________
1 None 0.04 0.04 0.02
2 The present 0.04 0.04 0.02
dye
3 The known 0.05 0.05 0.07
dye A
______________________________________
As is clear from the above table, in the case of the sample containing the present dye, decolorization rapidly took place. Moreover, the sample containing the present dye had no color stain as in the sample containing the known dye. Furthermore, response functions of these samples were obtained using square wave chart. As the result, it was found that the Sample No. 2 was extremely excellent than the Sample No. 1 and showed higher sharpness than the Sample No. 3.
Spectral reflection characteristic of the samples No. 2 and 3 was measured to obtain the following results.
______________________________________
Sample Dye Spectral reflection
maximum
______________________________________
2 The present dye 665 mμ
3 The known dye A 660 mμ
______________________________________
To 1 kg of the same green sensitive silver chlorobromide emulsion as used in a layer (3) of Sample No. 1 in Example 1 was added 25 ml of 2% aqueous solution of the dye (III) of the present invention as enumerated hereinbefore. In the same manner, another emulsion was prepared using the following known dye B in place of the dye (III). ##SPC8##
Using these emulsions, multilayer color photographic papers of samples No. 4 and 5 were produced in the same manner as production of Sample No. 1 in Example 1. That is, other layers were the same as those of Sample No. 1.
Samples No. 1, 4 and 5 were exposed and then subjected to the same processes as in Example 1. Thereafter, density of unexposed areas of these samples was measured. As shown in the following table, the sample containing the present dye was rapidly decolorized and showed no color stain.
______________________________________
Density of unexposed area
Sample Dye Blue Green Red
density density density
______________________________________
1 None 0.04 0.04 0.02
4 The present 0.04 0.04 0.02
dye
5 The known 0.05 0.07 0.02
dye B
______________________________________
Response functions of these samples were obtained using square wave chart to find that Sample No. 4 was extremely excellent than Sample No. 1 and showed substantially the same resolving power as Sample No. 5.
1 g of dye (II) of the present invention and 1 g of dye (VI) of the present invention were added to 1 l of 10% gelatin solution. To the mixture were further added 25 ml of 2% aqueous solution of chrome alum as a hardener and 20 ml of 5% aqueous solution of saponin. The resultant mixture was coated on a surface of a film which was opposite to the surface coated with a silver halide emulsion. This layer was excellent in the effect of preventing halation and was rapidly decolorized and dissolved out during developing process to cause no color stain caused due to remaining dye after process. Moreover, no decreasing of sensitivity and fog were caused during coating of the emulsion and storage of the film. Thus, it was found that this film having such unti-halation layer was an extremely excellent light-sensitive photographic material.
The density in the Examples was measured by Macbeth 514 densitometer.
Claims (7)
1. A silver halide photographic lightsensitive material having on one or both sides of a support a layer containing at least one of dyes represented by the general formula: ##SPC9##
(wherein X is selected from the group consisting of hydrogen atom, hydroxyl group, halogen atom and lower alkyl group; L is methine group which may be substituted with lower alkyl group at meso-position; M is selected from the group consisting of hydrogen atom, alkali metal and ammonium group; and n is 1 or 2).
2. A silver halide photographic lightsensitive material according to claim 1, which contains the dye in at least one of silver halide emulsion layer, intermediate layer and over-coating layer.
3. A silver halide photographic lightsensitive material according to claim 1, which contains the dye in at least one of under-coating layer and back-coating layer of the support.
4. A silver halide photographic lightsensitive material according to claim 1, which contains the dye in an amount of about 1 mg -- about 10 g/m2.
5. A silver halide photographic lightsensitive material according to claim 2, which contains the dye in an amount of about 1 mg -- about 100 mg/m2.
6. A silver halide photographic lightsensitive material according to claim 3, which contains the dye in an amount of about 10 mg -- about 10 g/m2.
7. A silver halide photographic lightsensitive material according to claim 1, wherein the dye has the following general formula: ##SPC10##
(wherein L, M and n are as defined above).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JA49-21524 | 1974-02-25 | ||
| JP2152474A JPS5510061B2 (en) | 1974-02-25 | 1974-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3932188A true US3932188A (en) | 1976-01-13 |
Family
ID=12057327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/552,262 Expired - Lifetime US3932188A (en) | 1974-02-25 | 1975-02-24 | Silver halide photographic lightsensitive material |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3932188A (en) |
| JP (1) | JPS5510061B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3984246A (en) * | 1974-11-09 | 1976-10-05 | Agfa-Gevaert, A.G. | Antihalation and filter dyes for photographic materials |
| US4110115A (en) * | 1976-05-06 | 1978-08-29 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive element having dyed layer |
| US4179294A (en) * | 1976-03-26 | 1979-12-18 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive element containing dye |
| US4877721A (en) * | 1986-05-15 | 1989-10-31 | Eastman Kodak Company | Photographic silver halide elements containing filter dyes |
| US4940654A (en) * | 1987-12-23 | 1990-07-10 | Eastman Kodak Company | Solid particle dispersion filter dyes for photographic compositions |
| US4988611A (en) * | 1988-06-30 | 1991-01-29 | Eastman Kodak Company | Imaging utilizing a light-handleable photographic element having solid particle dispersion filter dye layer |
| US5139930A (en) * | 1984-04-20 | 1992-08-18 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic light-sensitive material |
| US5252443A (en) * | 1992-02-03 | 1993-10-12 | Eastman Kodak Company | Means for assuring proper orientation of the film in an asymmetrical radiographic assembly |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2274782A (en) * | 1937-11-24 | 1942-03-03 | Chromogen Inc | Light-sensitive photographic material |
| US3502474A (en) * | 1965-07-28 | 1970-03-24 | Fuji Photo Film Co Ltd | Process for producing photographic light-sensitive elements |
| US3647460A (en) * | 1969-05-30 | 1972-03-07 | Agfa Gevaert Nv | Method of producing photographic images by rapid processing |
| US3746539A (en) * | 1971-02-09 | 1973-07-17 | Fuji Photo Film Co Ltd | Color photographic light-sensitive materials for color prints showingexcellent color reproduction |
| US3865817A (en) * | 1972-05-02 | 1975-02-11 | Fuji Photo Film Co Ltd | Oxonol dyes and process for preparing oxonol dyes |
-
1974
- 1974-02-25 JP JP2152474A patent/JPS5510061B2/ja not_active Expired
-
1975
- 1975-02-24 US US05/552,262 patent/US3932188A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2274782A (en) * | 1937-11-24 | 1942-03-03 | Chromogen Inc | Light-sensitive photographic material |
| US3502474A (en) * | 1965-07-28 | 1970-03-24 | Fuji Photo Film Co Ltd | Process for producing photographic light-sensitive elements |
| US3647460A (en) * | 1969-05-30 | 1972-03-07 | Agfa Gevaert Nv | Method of producing photographic images by rapid processing |
| US3746539A (en) * | 1971-02-09 | 1973-07-17 | Fuji Photo Film Co Ltd | Color photographic light-sensitive materials for color prints showingexcellent color reproduction |
| US3865817A (en) * | 1972-05-02 | 1975-02-11 | Fuji Photo Film Co Ltd | Oxonol dyes and process for preparing oxonol dyes |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3984246A (en) * | 1974-11-09 | 1976-10-05 | Agfa-Gevaert, A.G. | Antihalation and filter dyes for photographic materials |
| US4179294A (en) * | 1976-03-26 | 1979-12-18 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive element containing dye |
| US4110115A (en) * | 1976-05-06 | 1978-08-29 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive element having dyed layer |
| US5139930A (en) * | 1984-04-20 | 1992-08-18 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic light-sensitive material |
| US4877721A (en) * | 1986-05-15 | 1989-10-31 | Eastman Kodak Company | Photographic silver halide elements containing filter dyes |
| US4940654A (en) * | 1987-12-23 | 1990-07-10 | Eastman Kodak Company | Solid particle dispersion filter dyes for photographic compositions |
| US4988611A (en) * | 1988-06-30 | 1991-01-29 | Eastman Kodak Company | Imaging utilizing a light-handleable photographic element having solid particle dispersion filter dye layer |
| US5252443A (en) * | 1992-02-03 | 1993-10-12 | Eastman Kodak Company | Means for assuring proper orientation of the film in an asymmetrical radiographic assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50115815A (en) | 1975-09-10 |
| JPS5510061B2 (en) | 1980-03-13 |
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